EP0250212A1 - Verfahren zur Herstellung von Etheen-Propeen-Copolymerkautschuk - Google Patents

Verfahren zur Herstellung von Etheen-Propeen-Copolymerkautschuk Download PDF

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Publication number
EP0250212A1
EP0250212A1 EP87305345A EP87305345A EP0250212A1 EP 0250212 A1 EP0250212 A1 EP 0250212A1 EP 87305345 A EP87305345 A EP 87305345A EP 87305345 A EP87305345 A EP 87305345A EP 0250212 A1 EP0250212 A1 EP 0250212A1
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EP
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Prior art keywords
ethylene
propylene
compound
aluminum
catalyst component
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EP87305345A
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English (en)
French (fr)
Inventor
Satoshi Ueki
Kouji Maruyama
Haruo Mizukami
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Tonen General Sekiyu KK
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Toa Nenryo Kogyyo KK
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Publication of EP0250212A1 publication Critical patent/EP0250212A1/de
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Definitions

  • the process employs a solid catalyst component formed by contacting (1) a metal oxide, (2) a reaction product of a magnesium halide and a compound represented by the formula Me(OR) n X z-n , (3) a silicon compound represented by the formula below and (4) a titanium compound with one another.
  • the process employs a catalyst formed by diluting a composition represented by the formula Mg m Ti(OR n X p (ED) q (where X denotes a halogen and ED denotes an electron donor compound) with a metal oxide and activating the diluted composition with an organoaluminum compound.
  • the above-mentioned titanium-based catalyst supported on a metal oxide provides a copolymer which is improved to a certain extent in particle properties; however, it still has a disadvantage of forming the copolymer in a rather smaller quantity per unit weight thereof.
  • the present invention comprises copolymerizing ethylene and propylene with a catalyst component disclosed in EP-A-173470, the contents or which are hereby incorporated by reference.
  • the catalyst component exhibits outstanding performance in the production of crystalline polyethylene and crystalline copolymer of ethylene and a small amount of ⁇ -olefin. It is obtained by contacting (a) a metal oxide, (b) an organomagnesium compound, and (c) a hydrocarbyloxy group-containing compound with one another, and contact­ing the thus obtained contact product with (d) a titanium compound. This discovery led to the present invention.
  • Fig. 1 is a flowchart showing the process of the invention.
  • the gist of the present invention resides in a process for producing an ethylene-propylene copolymer rubber containing 15-90 mol% of ethylene, said process comprising copolymerizing ethylene and propylene in the presence of a polymerization catalyst composed of a catalyst component and an organoaluminum compound, said catalyst component being obtained by contacting (A) a metal oxide, (B) an organomagnesium compound, and (C) a hydrocarbyloxy group-containing compound with one another, and contacting the thus obtained contact product with (D) a titanium compound.
  • the metal oxide used in the present invention is preferably an oxide of a metal selected from the group of elements belonging to Groups II to IV of the periodic table. It includes, for example, B2O3, MgO, Al2O3, SiO2, CaO, TiO2, ZnO, ZrO2, SnO2, BaO, and ThO2. Preferable among them are B2O3, MgO, Al2O3, SiO2, TiO2, and ZrO2. Especially preferable is SiO2. Additional examples of the metal oxides are complex oxides containing these metal oxides, for example, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O3, SiO2-Cr2O3, and SiO2-TiO2-MgO.
  • the above-mentioned metal oxides and complex oxides should prefer strictlyably be anhydrous in principle. However, they may contain a very small amount of hydroxide which is usually present. In addition, they may contain impurities in such an amount that they do not considerably impair the properties of the metal oxides.
  • the permissible impurities are oxides, carbonates, sulfates, and nitrates such as sodium oxide, potassium oxide, lithium oxide, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium sulfate, aluminum sulfate, barium sulfate, potassium nitrate, magnesium nitrate, and aluminum nitrate.
  • metal oxides should preferably be in the form of a powder with low crystallinity that gives a broad X-ray diffraction pattern or an amorphous powder.
  • the particle size and shape of the powder should be properly controlled because they affect the form of the resulting olefin polymer.
  • the powder should have a great specific surface area, pore volume, and average pore diameter.
  • the metal oxide should preferably be calcined, prior to use, at as high a temperature as possible to remove poisonous substances, and the calcined metal oxide should be isolated from the atmosphere during handling.
  • the organomagnesium compound used in the present invention is preferably one represented by the formula RMgR ⁇ , wherein R denotes a hydrocarbon group (alkyl,cycloalkyl,aryl and aralkyl) having 1 to 20 carbon atoms, and R ⁇ denotes a hydrocarbon group (alkyl,cycloalkyl,aryl and aralkyl) having 1 to 20 carbon atoms or a halogen atom.
  • organomagnesium compound in which both R and R ⁇ are hydrocarbon groups examples are shown below.
  • organomagnesium compounds may be used in the form of mixture or complex compound with an organic compound of other metals which is represented by the formula MR n (wherein M denotes boron, beryllium, aluminum, or zinc; R denotes an alkyl, cycloalkyl, aryl, or aralkyl group having 1 to 20 carbon atoms; and n denotes the valence of the metal M).
  • M denotes boron, beryllium, aluminum, or zinc
  • R denotes an alkyl, cycloalkyl, aryl, or aralkyl group having 1 to 20 carbon atoms
  • n denotes the valence of the metal M.
  • Their examples include triethyl aluminum, tributyl aluminum, triisobutyl aluminum, triphenyl aluminum, triethyl boron, tributyl boron, diethyl beryllium, diisobutyl beryllium, diethyl
  • the amount of other metals is usually less than 2 gram atom, preferably less than 1 gram atom, for 1 gram atom of magnesium.
  • organomagnesium compound in which both R is a hydrocarbon group and R ⁇ is a halogen atom examples of the organomagnesium compound in which both R is a hydrocarbon group and R ⁇ is a halogen atom are shown below.
  • MgCl Magnetic chloride, magnesium bromide, and magnesium iodide
  • the hydrocarbyloxy group-containing compound used in the present invention is preferably represented by the formula X m C(OR) 4-m (wherein X denotes a hydrogen atom, a halogen atom, or a hydrocarbon group (alkyl, cycloalkyl, aryl or alalkyl) having 1 to 20 carbon atoms or a halogen-­substituted compound thereof; R denotes an alkyl, cycloalkyl, aryl, or alalkyl group having 1 to 20 carbon atoms; and m denotes a number of 0, 1, or 2. Examples of the hydrocarbyloxy group-containing compound in which m is 0, 1, and 2 are given below.
  • C(OR)4 such as orthocarbonic acid ester in which R is a methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, hexyl, octyl, cyclohexyl, or phenyl group.
  • XC(OR)3 such as orthoformic acid ester in which R is a methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, cyclohexyl, or phenyl group (with X being a hydrogen atom); methyl orthoacetate, ethyl orthoacetate, methyl orthopropionate, butyl orthopropionate, C4H11C(OC2H3)3, C6H3C(OCH3)3, C6H3C(CC2H3)3, C6H3C(OC3H7)3, C7H7C(OC2H3)3, and C8H9C(OC2H3)3 (with X being a hydrocarbon group); ethyl orthobromoacetate, ethyl orthochloroacetate, ethyl ortho- ⁇ -bromopropionate, and ethyl ortho- ⁇ -chloropropionate (with X being a hydrocarbon group);
  • X2C(OR)2 such as ethylidene dimethyl ether, ethylidene diethyl ether, methylal, methylene diethyl ether, mono­chloroacetal, dichloroacetal, trichloroacetal, monobromoacetal, mono­iodoacetal, and benzaldehyde diethylacetal.
  • Preferable among the above-mentioned compounds are lower alkyl esters of orthocarbonic acid such as methyl orthocarbonate ethyl orthocarbonate, and butyl orthocarbonate; lower alkyl esters of orthoformic acid such as methyl orthoformate, ethyl orthoformate, and butyl orthoformate; and lower alkyl esters of orthoacetic acid such as methyl orthoacetate, ethyl orthoacetate, and butyl orthoacetate.
  • orthocarbonic acid such as methyl orthocarbonate ethyl orthocarbonate, and butyl orthocarbonate
  • lower alkyl esters of orthoformic acid such as methyl orthoformate, ethyl orthoformate, and butyl orthoformate
  • lower alkyl esters of orthoacetic acid such as methyl orthoacetate, ethyl orthoacetate, and butyl orthoacetate.
  • the titanium compound is divalent, trivalent, or tetravalent titanium compound.
  • Their examples include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium, dichlorodiethyoxytitanium, dichlorodibutoxytitanium, dichlorodiphenoxy­titanium, chlorotriethoxytitanium, chlorotributoxytitanium, tetrabutoxy­titanium, and titanium trichloride.
  • titanium tetrachloride tetra­valent titanium halides
  • titanium tetrachloride trichloroethoxy­titanium, dichlorodibutoxytitanium, and dichlorodiphenoxytitanium.
  • titanium tetrachloride tetra­valent titanium halides
  • trichloroethoxy­titanium trichloroethoxy­titanium
  • dichlorodibutoxytitanium dichlorodiphenoxytitanium
  • dichlorodiphenoxytitanium tetra­valent titanium halides
  • titanium tetrachloride trichloroethoxy­titanium
  • dichlorodibutoxytitanium dichlorodiphenoxytitanium
  • the preparation of the catalyst component used in the present invention involves the steps of contacting a metal oxide (referred to as component A hereinafter), an organomagnesium compound (referred to as component B hereinafter), and a hydrocarbyloxy group-containing compound (referred to as component C hereinafter) with one another, and contact­ ing the resulting contact product with a titanium compound (referred to as component D hereinafter).
  • component A metal oxide
  • component B organomagnesium compound
  • component C hydrocarbyloxy group-containing compound
  • the first method is preferable.
  • the above-mentioned contacting may be accomplished by mixing and stirring or mechanically copulverizing the three components in the presence or absence of an inert medium.
  • the inert medium include hydrocarbons such as pentane, hexane, heptane, octane, decane, cyclohexane, benzene, toluene, and xylene; and halogenated hydrocarbons such as 1,2-dichloroethane, 1,2-dichloropropane, carbon tetrachloride, butyl chloride, isoamyl chloride, bromobenzene, and chlorotoluene.
  • the contacting of components A,B and C with one another is preferably performed at -20°C to +150°C preferably for 0.1 to 100 hours, more preferably at room temperature to 110°C for eg. 0.5 to 10 hours.
  • the contacting involves heat generation, it may be performed in such a manner that the components are mixed little by little at a low temperature in the initial stage, and after the mixing of the entire components is complete, the temperature is raised and contacting is continued.
  • the contact product may be washed with one of the above-mentioned inert media.
  • a ratio of components A, B and C for contact may be as follows: A/B - 1 g/0.1 to 100 mmol, preferably 1 g/1 to 10 mmol.
  • A/C 1 g/2 to 100 mmol, preferably 1 g/10 to 50 mmol.
  • C/B (molar ratio) 0.05 to 100, preferably 0.1 to 50.
  • product I solid product
  • a proper cleaning agent e.g., one of the above-mentioned inert media
  • the contacting of product I with component D may be accomplished by mixing and stirring or mechanically copulverising them in the presence or absence of an inert medium. Contacting by mixing and stirring in the presence of an inert medium is preferable. One of the above-mentioned inert media may also be used.
  • the ratio of contacting product I with component D is preferably more than 0.01 gram-mol, preferably 0.1 to 10 gram-mol for 1 gram-atom of magnesium in product I.
  • Their contacting may be performed at 0°C to 200°C for eg 0.5 to 20 hours, preferably at 60°C to 150°C and preferably for 1 to 5 hours in the case of mixing and stirring in the presence of an inert medium.
  • the contacting of product I with component D may be performed twice or more in the same manner as mentioned above. If necessary, the previous contact product may be washed with an inert medium, and component D (and the medium) may be freshly added.
  • the contact reaction product obtained as mentioned above may be washed, if necessary, with a hydrocarbon such as hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene, followed by drying, if necessary, before it is used as the catalyst component in the present invention.
  • a hydrocarbon such as hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene
  • the polymerization catalyst used in the present invention is a combination of the catalyst component obtained as mentioned above and an organoaluminum compound.
  • the usuable organoaluminum compound is preferably represented by the formula R n AlX 3-n (wherein R is an alkyl or aryl group; X is a halogen atom, alkoxyl group, or hydrogen atom; and n is a number in the range of 1 ⁇ n ⁇ 3).
  • the examples are alkyl aluminum compounds having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as trialkyl aluminum, dialkyl aluminum monohalide, monoalkyl aluminum dihalide, alkyl aluminum sesquihalide, dialkyl aluminum monoalkoxide, and dialkyl aluminum monohydride, and mixtures thereof and complex compounds thereof.
  • trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, and trihexyl aluminum
  • dialkyl aluminum monohalide such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide, and diisobutyl aluminum chloride
  • monoalkyl aluminum dihalide such as methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, and isobutyl aluminum dichloride
  • alkyl aluminum sesquihalide such as ethyl aluminum sesquichloride
  • dialkyl aluminum monoalkoxide such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, and di
  • trialkyl aluminum compounds particularly triethyl aluminum and triisobutyl aluminum.
  • the trialkyl aluminum may be used in combination with other organoaluminum compounds such as commercially available diethyl aluminum chloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum ethoxide, and diethyl aluminum hydride, or a mixture thereof or a complex compound thereof.
  • Another organoaluminum compound that can be used is one in which two or more aluminum atoms are connected through an oxygen atom or nitrogen atom.
  • Examples of such compounds are (C2H5)2AlOAl(C2H5)2, (C4H9)2AlOAl(C4H9)2, and
  • the organoaluminum compounds may be used alone or in combination with an electron donor compound.
  • the electron donor compound may be any of carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, alcoholates, phosphamides, thioethers, thioesters, carbonic acid esters, and compounds of phosphorus, arsenic, or antimony attached to an organic group through a carbon or oxygen atom.
  • Other electron donor compounds that can be used include organosilicon compounds and those compounds containing a hetero atom such as nitrogen, sulfur, oxygen, and phosphorus.
  • Two or more kinds of the electron donor compounds may be used. They may be used when the catalyst component is combined with an organo­aluminum compound or used after the contacting with an organoaluminum compound.
  • the organoaluminum compound is used usually in an amount of 1 to 2000 gram-mol, particularly 20 to 500 gram-mol, per gram-atom of titanium in the catalyst component of the present invention.
  • the amount of the organaluminum compound is preferably 0.1 to 40 gram-atom, more preferably 1 to 25 gram-atom in terms of aluminum per mol of the electron donor compound.
  • the catalyst component used in the present invention may be in the form of combination with an ethylene polymer and/or propylene polymer formed by preliminary polymerization in the presence of an organo­aluminum compound and, if necessary, an electron donor compound.
  • the amount of the polymer is preferably 0.1 to 100g, more preferably 1 to 50g, for 1g of the catalyst component.
  • the preliminary polymerisation my be performed by the ordinary process for the polymerization of the olefins with a Ziegler-Natta catalyst.
  • the copolymerization of ethylene and propylene may be performed in the same way that ethylene and propylene are copolymerized with a common Ziegler-Natta catalyst.
  • the preferred copolymerization process is the bulk polymerization that employs propylene as a medium and the gas-phase polymerization.
  • the copolymerization is preferably performed at -80°C to +150°C, more preferably 0°C to 80°C, and preferably under a pressure up to 60 atm.
  • the ethylene-propylene copolymer rubber obtained by the process of the present invention contains 15-90 mol% of ethylene. This ethylene content may be obtained when the ethylene/propylene molar ratio is 0.01-1.0 (in liquid phase) in the case of bulk polymerization in a medium of propylene or 0.03-3.0 in the case of gas-phase polymerization.
  • the copolymerization may be performed continuously or batchwise in one step or in two or more steps.
  • the process of the present invention generally provides in high yields an ethylene-propylene copolymer rubber having good particle properties, which does not need the step for removing the catalyst.
  • the ethylene content in the polymer was determined by infrared spectrophotometry.
  • Melt index (MI) was measured according to ASTM D1238, and bulk density was measured according to ASTM D1895-69, method A.
  • Heat of fusion was measured with DSC IIc made by Perkin-­Elmer Co., Ltd. True density was measured according to ASTM D1505.
  • SiO2 silicon oxide
  • G-952 a product of DAVISON, having a specific surface area of 302 m2/g, a pore volume of 1.54 cm3/g, and an average pore radius of 204 A.
  • BEM n-butylethyl magnesium
  • MAGALA BEM a product of Texas Alkyls, the solution containing 26.8 mmol of BEM
  • the resulting suspension was cooled to room temperature. To the suspension was added dropwise 50 ml of n-hexane and 20 ml of ethyl orthoformate, followed by stirring at 50°C for 1 hour. The supernatant liquid was discarded and the solid product was washed three times with 50 ml of n-hexane at 50°C.
  • Copolymerization was carried out at 20°C. One hour later, the autoclave was depressured and the resulting polymer was discharged, followed by drying.
  • the polymerization activity was 26.3 kg/g-catalyst component (a)-hour.
  • the polymer thus obtained was in the form of spherical granules. It has the following characteristic properties. Bulk density: 0.33 g/cm3 Melt index: 0.23 g/10 min True density: 0.863 g/cm3 Ethylene content: 55 mol% According to the differential thermal analysis, the polymer was found to have no Tm attributable to the ethylene chain. In addition, the polymer did not give a peak at 730 cm ⁇ 1 characteristic of crystalline poly­ethylene in IR spectrometry.
  • Catalyst component (b) containing 3.6% of titanium was prepared in the same manner as in Example 1, except that BEM was replaced by n-butylmagnesium chloride.
  • Catalyst component (c) containing 5.7% of titanium was prepared in the same manner as in Example 1, except that the SiO2 was replaced by Al2O3 formed by calcination in a nitrogen stream at 200°C for 2 hours and subsequently at 700°C for 5 hours.
  • Catalyst components (d) and (e) were prepared in the same manner as in Example 1, except that the ethyl orthoformate was replaced by the following hydrocarbyloxy group-containing compound.
  • Catalyst components (f) and (g) were prepared in the same manner as in Example 1, except that the ethyl orthoformate was replaced by the following hydrocarbyloxy group-containing compound.
  • Catalyst components (h) and (i) were prepared in the same manner as in Example 1, except that the BEM was replaced by the organomagnesium compound shown below.
  • Catalyst component (j) containing 5.4% of titanium was prepared in the same manner as in Example 1, except that the BEM was replaced by di-n-hexyl-Mg and the ethyl orthoformate was replaced by ethyl ortho­acetate.
  • Copolymerization of ethylene and propylene was performed in the same manner as in Example 1, except that the catalyst component prepared by preliminary polymerization as mentioned above was used and the conditions of copolymerization were changed as shown in Table 1. The results are shown in Table 1.
  • the preliminary polymerization of ethylene was performed in the same manner as in Example 18, except that 0.5 g of catalyst component (b) prepared in Example 7 was used and 0.5 mmol of TEAL was used.
  • the resulting catalyst component was found to contain 3.1 g of preliminary polymer per g of catalyst component (b).
  • Example 2 8 g of the SiO2 used in Example 1 (calcined at 600°C for 5 hours in a nitrogen atmosphere) was mixed with 50 ml of n-hexane. To the result­ing slurry was added dropwise 3.1 ml of 20% hexane solution of TEAL over 15 minutes. Nitrogen gas was blown into the mixture at 60°C for 4 hours to give a free-flowing powder.
  • the thus treated SiO2 powder was added to the solution obtained as mentioned above, followed by stirring for 15 minutes. Nitrogen gas was blown at 60°C for 4 hours to yield a dry, powdery catalyst component (m) containing 4.1% of titanium.
EP87305345A 1986-06-16 1987-06-16 Verfahren zur Herstellung von Etheen-Propeen-Copolymerkautschuk Withdrawn EP0250212A1 (de)

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JP138255/86 1986-06-16
JP13825586A JPS62295909A (ja) 1986-06-16 1986-06-16 エチレン・プロピレン共重合体ゴムを製造する方法

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0261808A2 (de) * 1986-08-25 1988-03-30 Tonen Corporation Verfahren zur Herstellung von kautschukartigen Ethen-Propen-Copolymeren
EP0208524B1 (de) * 1985-07-05 1990-05-16 Tonen Corporation Katalysatorbestandteil für Olefinpolymerisation
EP0437264A1 (de) * 1990-01-10 1991-07-17 Montell North America Inc. Bestandteile und Katalysatoren für die Olefinpolymerisation
EP0701575A4 (de) * 1992-10-19 1995-09-21 Mobil Oil Corp Hochaktive polyethylenkatalysatoren
EP1108728A1 (de) * 1999-12-17 2001-06-20 BP Chemicals S.N.C. Hochaktive Polyethylenkatalysatoren hergestellt mittels Alkoxykohlenstoff-Reagentien

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005054350A1 (ja) 2003-12-03 2005-06-16 Tonen Chemical Corporation 複合微多孔膜及びその製造方法並びに用途

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0014523B1 (de) * 1979-01-10 1983-03-30 Imperial Chemical Industries Plc Olefin-Polymerisationskatalysator und seine Herstellung und Verwendung
US4496660A (en) * 1980-10-01 1985-01-29 The Dow Chemical Company Catalyst prepared from organo-magnesium compound; oxygen- or nitrogen-containing compound; halide source; transition metal compound and reducing agent
EP0173470B1 (de) * 1984-07-31 1991-03-20 Tonen Corporation Katalysatorbestandteil für Olefinpolymerisation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0014523B1 (de) * 1979-01-10 1983-03-30 Imperial Chemical Industries Plc Olefin-Polymerisationskatalysator und seine Herstellung und Verwendung
US4496660A (en) * 1980-10-01 1985-01-29 The Dow Chemical Company Catalyst prepared from organo-magnesium compound; oxygen- or nitrogen-containing compound; halide source; transition metal compound and reducing agent
EP0173470B1 (de) * 1984-07-31 1991-03-20 Tonen Corporation Katalysatorbestandteil für Olefinpolymerisation

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0208524B1 (de) * 1985-07-05 1990-05-16 Tonen Corporation Katalysatorbestandteil für Olefinpolymerisation
EP0261808A2 (de) * 1986-08-25 1988-03-30 Tonen Corporation Verfahren zur Herstellung von kautschukartigen Ethen-Propen-Copolymeren
EP0261808A3 (de) * 1986-08-25 1990-01-17 Tonen Corporation Verfahren zur Herstellung von kautschukartigen Ethen-Propen-Copolymeren
EP0437264A1 (de) * 1990-01-10 1991-07-17 Montell North America Inc. Bestandteile und Katalysatoren für die Olefinpolymerisation
AU644123B2 (en) * 1990-01-10 1993-12-02 Montell North America Inc. Components and catalysts for the polymerization of olefins
CN1040118C (zh) * 1990-01-10 1998-10-07 蒙特尔北美公司 烯烃聚合的催化剂组分和催化剂
EP0701575A4 (de) * 1992-10-19 1995-09-21 Mobil Oil Corp Hochaktive polyethylenkatalysatoren
EP0701575A1 (de) * 1992-10-19 1996-03-20 Mobil Oil Corporation Hochaktive polyethylenkatalysatoren
EP1108728A1 (de) * 1999-12-17 2001-06-20 BP Chemicals S.N.C. Hochaktive Polyethylenkatalysatoren hergestellt mittels Alkoxykohlenstoff-Reagentien
WO2001044320A1 (en) * 1999-12-17 2001-06-21 Bp Chemicals Limited High activity polyethylene catalysts prepared with alkoxycarbon reagents

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JPS62295909A (ja) 1987-12-23

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